WO2022057919A1 - 正极材料、正极片及电池 - Google Patents
正极材料、正极片及电池 Download PDFInfo
- Publication number
- WO2022057919A1 WO2022057919A1 PCT/CN2021/119309 CN2021119309W WO2022057919A1 WO 2022057919 A1 WO2022057919 A1 WO 2022057919A1 CN 2021119309 W CN2021119309 W CN 2021119309W WO 2022057919 A1 WO2022057919 A1 WO 2022057919A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- positive electrode
- lithium iron
- manganese phosphate
- iron manganese
- phosphate material
- Prior art date
Links
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 claims abstract description 181
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims abstract description 114
- 239000002245 particle Substances 0.000 claims abstract description 76
- 239000011164 primary particle Substances 0.000 claims description 24
- 239000013078 crystal Substances 0.000 claims description 21
- 239000011267 electrode slurry Substances 0.000 description 20
- 239000011572 manganese Substances 0.000 description 19
- 238000005056 compaction Methods 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 239000006258 conductive agent Substances 0.000 description 9
- 238000009792 diffusion process Methods 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 239000011163 secondary particle Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- -1 lithium iron manganese tetraphosphate Chemical compound 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910015835 LiMn0.65Fe0.35PO4 Inorganic materials 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- BKKSQIVXDIVZHC-UHFFFAOYSA-H P(=O)([O-])([O-])[O-].[Fe+2].[Mn+2].[Fe+2].P(=O)([O-])([O-])[O-] Chemical compound P(=O)([O-])([O-])[O-].[Fe+2].[Mn+2].[Fe+2].P(=O)([O-])([O-])[O-] BKKSQIVXDIVZHC-UHFFFAOYSA-H 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- DOCYQLFVSIEPAG-UHFFFAOYSA-N [Mn].[Fe].[Li] Chemical compound [Mn].[Fe].[Li] DOCYQLFVSIEPAG-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229940071264 lithium citrate Drugs 0.000 description 1
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 description 1
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
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- H01M10/052—Li-accumulators
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- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present application relates to the technical field of batteries, in particular to a positive electrode material, a positive electrode sheet and a battery.
- the cathode material of lithium-ion batteries is critical to the performance of the battery.
- the cathode materials commonly used in power batteries include ternary materials, lithium iron phosphate materials, and lithium manganese iron phosphate materials.
- lithium manganese iron phosphate (LMFP for short) has higher safety and cyclability than ternary materials, and the potential of LMFP is much higher. Due to lithium iron phosphate (the potential of lithium iron phosphate is 3.4V), it is expected to improve the energy density of the battery. Therefore, the lithium iron manganese phosphate material with higher safety and higher energy density has gradually become the mainstream cathode material for power batteries.
- the common product forms of LMFP on the market are mainly single-crystal-like and agglomerate.
- the single-crystal-like material is composed of one or a few (no more than 5) primary particles, with very few internal grain boundaries; agglomerates
- the material is a secondary particle material formed by agglomeration of many primary particles, and there are many internal grain boundaries.
- the primary particles of single-crystal LMFP-like materials are relatively large, so that the degree of manganese dissolution of such materials during the battery cycle is low, but their capacity is low under the same metal ratio; while the primary particles of agglomerates are small and the specific surface area is small.
- the present application provides a positive electrode material, a positive electrode sheet and a battery, wherein the positive electrode material adopts five kinds of LMFP materials whose D50 particle size decreases in turn, and the morphology, particle number ratio and specificity of the five kinds of LMFP materials are further controlled.
- the size of D 50 can make the positive electrode sheet using the positive electrode material have a higher compaction density, and the battery with the positive electrode sheet can take into account the performance of high capacity, low dissolved manganese content, and high cycle stability.
- the present application provides a positive electrode material
- the positive electrode material includes a first lithium iron manganese phosphate material, a second lithium iron manganese phosphate material, a third lithium iron manganese phosphate material, and a fourth iron manganese iron phosphate material.
- the particle number ratio of the fifth lithium iron manganese phosphate material is (0.8-1.2):(0.8-1.2):(1.6-2.4):(6.4-9.6):(6.4-9.6) the first iron manganese phosphate Lithium material, the second lithium manganese iron phosphate material, the third lithium iron manganese phosphate material, the fourth lithium iron manganese phosphate material, and the fifth lithium iron manganese phosphate material; wherein the first lithium iron manganese phosphate material is an agglomerate,
- the fourth lithium iron manganese phosphate material and the fifth lithium iron manganese phosphate material are both quasi-single crystals, and the second lithium iron manganese phosphate material and the third lithium iron manganese phosphate material are aggregates and
- the D 50 1 to D 50 5 sequentially represent the value of the particle size D50 of the first lithium iron manganese phosphate material to the fifth lithium iron manganese phosphate material, in units of ⁇ m; the value of a The range is 0.35-0.5, the value range of the b is 0.2-0.27, the value range of the c is 0.17-0.18, and the value range of the d is 0.15-0.16.
- the present application provides a positive electrode slurry, the positive electrode slurry includes the positive electrode material described in the first aspect of the present application, a conductive agent and a solvent.
- the present application provides a positive electrode sheet, the positive electrode sheet includes a current collector and a positive electrode material layer disposed on the current collector, the positive electrode material layer includes the positive electrode material described in the first aspect of the present application, Or coated with the positive electrode slurry described in the second aspect of the present application.
- the present application provides a battery including the positive electrode sheet described in the third aspect of the present application.
- the beneficial effects of the present application include: when the five kinds of lithium manganese iron phosphate materials contained in the positive electrode material provided by the present application meet the above-mentioned specific D50 particle size relationship, the above-mentioned specific morphology requirements and specific particle number ratio requirements, the positive electrode material can be used for
- the positive electrode slurry prepared from the material has good viscosity and stability
- the positive electrode sheet made from the positive electrode material has a higher compaction density
- the battery with the positive electrode sheet has higher capacity and higher cycle stability at the same time.
- low dissolved manganese and other excellent electrical properties when the five kinds of lithium manganese iron phosphate materials contained in the positive electrode material provided by the present application meet the above-mentioned specific D50 particle size relationship, the above-mentioned specific morphology requirements and specific particle number ratio requirements.
- an embodiment of the present application provides a positive electrode material, and the positive electrode material includes a first lithium iron manganese phosphate material, a second lithium iron manganese phosphate material, a third lithium iron manganese phosphate material, and a fourth manganese iron phosphate material.
- Lithium iron material and fifth lithium iron manganese phosphate material the first lithium iron manganese phosphate material, the second lithium iron manganese phosphate material, the third lithium iron manganese phosphate material, and the fourth lithium iron manganese phosphate material
- the particle number ratio of the material and the fifth lithium iron manganese phosphate material is (0.8-1.2):(0.8-1.2):(1.6-2.4):(6.4-9.6):(6.4-9.6) first manganese phosphate Lithium iron material, the second lithium iron manganese phosphate material, the third lithium iron manganese phosphate material, the fourth lithium iron manganese phosphate material, and the fifth lithium iron manganese phosphate material; wherein, the first lithium iron manganese phosphate material is an agglomerate, and the third lithium iron manganese phosphate material is an agglomerate.
- the lithium iron manganese tetraphosphate material and the fifth lithium iron manganese phosphate material are both quasi-single crystals, and the second lithium iron manganese phosphate material and the third lithium iron manganese phosphate material are aggregates and/or quasi-single crystals, respectively, and satisfy the following grains: Diameter relationship:
- D 50 1 to D 50 5 represent the values of particle size D 50 of the first lithium iron manganese phosphate material to the fifth lithium iron manganese phosphate material in sequence, and the unit is ⁇ m; the value range of a is 0.35 -0.5, the value range of b is 0.2-0.27, the value range of c is 0.17-0.18, and the value range of d is 0.15-0.16.
- the above-mentioned D 50 1 to D 50 5 can be regarded as the particle size of the respective secondary particles in order (if the LMFP-based single crystal material consists of one primary particle, it can also be regarded as a "secondary particle") .
- LMFP materials with different morphologies and different particle size D 50 values affect the length of the diffusion path of lithium ions, the amount of dissolved Mn, and the cycle stability.
- the first lithium manganese iron phosphate material in the form of agglomerates has many grain boundaries, and the energy barrier to be overcome by the diffusion of lithium ions in it is large, but the particle size of the primary particles that make it up is small, and the diffusion path of lithium ions in it is short.
- the fourth and fifth lithium manganese iron phosphate materials in quasi-single-crystal form have large primary particle size, long diffusion paths for lithium ions, but few grain boundaries and small diffusion energy barriers. Therefore, in the above morphology Under the combined effect of the requirements and D 50 particle size requirements, the charge and discharge capabilities of the above five kinds of lithium manganese iron phosphate materials can be basically the same.
- the compaction density of the positive electrode sheet will still be low even under the combination of the above-mentioned various particles of different sizes; If the D 50 1 of the lithium material is too small, its primary particle size is lower, the specific surface area of the material will increase, and the side reaction between it and the electrolyte will increase, and the structural stability of the material during the cycle will become worse. The amount of dissolved Mn increases.
- the compaction density of the positive electrode sheet will also be reduced to a certain extent; , The particle size of the fifth lithium iron manganese phosphate material will also be large, which will lengthen the diffusion path of lithium ions in these two materials and reduce the rate performance of the battery.
- the value range of the a is 0.41 ⁇ a ⁇ 0.45, and the value range of the b is 0.21 ⁇ b ⁇ 0.23.
- the a is 0.41, the b is 0.23, the c is 0.18, and the d is 0.16.
- the second lithium iron manganese phosphate material and the third lithium iron manganese phosphate material are aggregates and/or quasi-single crystals respectively" can be understood as the second lithium iron manganese phosphate material is aggregates or quasi-single crystals or both. It contains agglomerates and quasi-single crystals.
- the third lithium iron manganese phosphate material is agglomerates or quasi-single crystals or contains both agglomerates and quasi-single crystals.
- the median diameter of the primary particles of the agglomerates is in the range of 100 nm-500 nm. That is, the median diameter of the primary particles of the first lithium iron manganese phosphate material is in the range of 100nm-500nm, and the median diameter of the primary particles of the second lithium iron manganese phosphate material in the form of agglomerates is in the range of 100nm-500nm range, the median particle diameter of the primary particles of the third lithium iron manganese phosphate material in the form of agglomerates is in the range of 100 nm-500 nm.
- the agglomerates in the above-mentioned median particle size range can avoid the increase in the number of primary particles constituting the secondary particles of the LMFP material, resulting in an increase in the specific surface area of the secondary particles, thereby avoiding an increase in the specific surface area of the secondary particles.
- the area where side reactions occur increases; at the same time, the crushing rate of secondary particles can be reduced in the process of pressing the positive electrode sheet, thereby avoiding the problem of causing new interfaces to appear and deteriorating battery performance; on the other hand, the above median particle size range
- the agglomerates can reduce the diffusion path of lithium ions in the secondary particle material, thereby avoiding the problems that the capacity of the LMFP material is low, the battery impedance increases, and the power performance decreases.
- the median particle size of the agglomerates is in the above range, which can avoid the increase of side reactions with the electrolyte due to the too small primary particles of the agglomerates, thereby avoiding the deterioration of the structural stability of the agglomerates and the increase in the amount of dissolved Mn.
- the diffusion path of lithium ions in the agglomerates can be more suitable, so that the battery rate performance is better.
- the primary particle size of the single crystal-like is in the range of 0.5 ⁇ m-2.5 ⁇ m. In this way, it can avoid that the single-crystal-like primary particles are too large and the diffusion path of lithium ions is lengthened, and the rate performance of the battery is deteriorated.
- the primary particle size of the fourth lithium iron manganese phosphate material and the fifth lithium iron manganese phosphate material may both be in the range of 1.5 ⁇ m-2.5 ⁇ m, and the third phosphoric acid in the form of a single crystal
- the median particle size of the primary particles of the lithium manganese iron material is in the range of 1.0 ⁇ m-1.5 ⁇ m
- the median particle size of the primary particles of the second lithium iron manganese phosphate material in the quasi-single crystal form is in the range of 0.5 ⁇ m-1.0 ⁇ m.
- the particle number ratio of the first lithium iron manganese phosphate material, the second lithium iron manganese phosphate material, the third lithium iron manganese phosphate material, the fourth lithium iron manganese phosphate material and the fifth lithium iron manganese phosphate material may be is (0.8-1.2):(0.8-1.2):(1.6-2.4):(6.4-9.6):(6.4-9.6).
- the positive electrode sheet made from the above-mentioned positive electrode material can have a higher compaction density (2.55 g/cm 3 or more).
- the first lithium iron manganese phosphate material, the second lithium iron manganese phosphate material, the third lithium iron manganese phosphate material, the fourth lithium iron manganese phosphate material, and the fifth lithium iron manganese phosphate material The particle number ratio is 1:1:2:8:8. In this way, the positive electrode sheet can have a very high compaction density (eg, about 2.9 g/cm 3 ). Further, the mass ratio of the first lithium iron manganese phosphate material, the second lithium iron manganese phosphate material, the third lithium iron manganese phosphate material, the fourth lithium iron manganese phosphate material and the fifth lithium iron manganese phosphate material may be 100. :14:2.5:0.5:0.3.
- the surfaces of the above-mentioned first to fifth lithium iron manganese phosphate materials may all have a carbon coating layer, so that the electrical conductivity of each of the lithium iron manganese phosphate materials can be improved.
- the molar ratio of manganese to iron (Mn/Fe ratio) in the first lithium iron manganese phosphate material to the fifth lithium iron manganese phosphate material is in the range of 1.0-7.4.
- the Mn/Fe ratios in the five lithium iron manganese phosphate materials can be equal or unequal, which is not specifically limited.
- the LMFP materials in the form of agglomerates can be prepared in the following manner:
- the raw materials for synthesizing LMFP ie, manganese source, iron source, phosphorus source, lithium source and carbon source
- LMFP manganese source, iron source, phosphorus source, lithium source and carbon source
- the sintering process sequentially includes a first heating section, a first constant temperature section, a second heating section, a second constant temperature section and a cooling section; wherein, The first heating section is from room temperature to the first constant temperature (such as 400°C), and the heating time can be 2.5h-3.5h; the constant temperature time of the first constant temperature section is 3.5h-5.5h; the second heating section is The first constant temperature (such as 400 ° C) rises to the second constant temperature (such as 700 ° C), and the heating time can be 2.5h-4.0h; the constant temperature time of the second constant temperature section can be 2.5h-4.5h; The second constant temperature (such as 750°C) is lowered to about 50°C, and the cooling time is 5.5h-7.5h.
- the first constant temperature such as 400 ° C
- the constant temperature time of the first constant temperature section is 3.5h-5.5h
- the second heating section is The first constant temperature (such as 400 ° C) rises to the second constant temperature (such as 700 ° C), and
- the sintered material is subjected to airflow crushing, wherein the pressure of the airflow crushing can be 3MPa-5MPa, and the time can be 2h-3h; then screen and classify to obtain the material with the desired particle size D 50 .
- the mixing time in the above step (1), may be 0.5h-1.5h, and according to another embodiment of the present application, the mixing time in the above step (1) may be 0.75h-1.2 h.
- ferromanganese phosphate can be selected as the manganese source, iron source and phosphorus source at the same time.
- the lithium source may include, but is not limited to, at least one of lithium hydroxide, lithium carbonate, lithium nitrate, lithium oxalate, lithium dihydrogen phosphate, lithium citrate, and lithium acetate.
- the carbon source includes, but is not limited to, at least one of glucose, sucrose, starch, fructose, citric acid, ascorbic acid, and polyethylene glycol.
- a grinding medium with a diameter of 0.6mm-0.8mm may be used to grind the material until the particle size of the material is below 50 ⁇ m, and then a grinding medium with a diameter of 0.1mm-0.3mm may be used for grinding. The medium is milled until the particle size of the material is 40nm-60nm.
- the inlet temperature during spray drying can be 150°C-200°C, and according to another embodiment of the present application, the inlet temperature during spray drying is 160°C-180°C .
- the above-mentioned preparation methods of the quasi-single-crystal LMFP material and the LMFP material of the agglomerate form are different in that the first constant temperature and the second constant temperature during sintering are different, and the pressure of airflow crushing is different.
- the first heating section is raised from room temperature to a first constant temperature (such as 450°C), and the heating time can be 2.5h-3.5h; the first constant temperature The constant temperature time of the heating section is 3.5h-5.5h; the second heating section is from the first constant temperature (such as 450°C) to the second constant temperature (eg 750°C), and the heating time can be 2.5h-4.0h; The constant temperature time of the constant temperature section can be 2.5h-4.5h; the cooling section is from the second constant temperature (such as 750°C) to about 50°C, and the cooling time is 6.5h-8.5h.
- airflow crushing can be carried out under the pressure of 5MPa-8MPa for 2h-3h;
- an embodiment of the present application further provides a positive electrode slurry, the positive electrode slurry includes the above-mentioned positive electrode material and a conductive agent, a binder and a solvent.
- the mass ratio of the positive electrode material, the conductive agent and the binder is 100:(0.5-5):(0.5-5).
- the solid content of the positive electrode slurry is 10wt%-80wt%.
- the conductive agent includes at least one of carbon nanotubes, conductive carbon black, and graphene, and according to another embodiment of the present application, the conductive agent includes three of carbon nanotubes, conductive carbon black, and graphene.
- the three-dimensional conductive agent can make the positive electrode material layer formed by the positive electrode slurry have better conductivity. Further, the mass ratio of carbon nanotubes, conductive carbon black and graphene may be 6:5:2.
- the binder is a conventional choice in the battery field, for example, it can be selected from polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), styrene butadiene rubber (SBR), polypropylene
- PVDF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- PVA polyvinyl alcohol
- SBR styrene butadiene rubber
- PAN polyimide
- PAA polyacrylic acid
- CMC sodium carboxymethylcellulose
- alginate sodium alginate
- PVDF can refer to a copolymer obtained by copolymerizing vinylidene fluoride and an olefin compound containing a polar group
- the polar group includes at least one of a carboxyl group, an epoxy group, a hydroxyl group and a sulfonic acid group.
- the presence of agglomerates can enhance the peel strength between the cathode coating formed by the cathode slurry and the current collector.
- the solvent is a conventional choice in the battery field, for example, N-methylpyrrolidone (NMP) is used.
- NMP N-methylpyrrolidone
- the positive electrode slurry may further contain a dispersant, so as to better improve the dispersibility and stability of the positive electrode slurry.
- the dispersant may be polyvinylpyrrolidone (PVP) or the like.
- the first LMFP material, the second LMFP material and the third LMFP material with larger particle size can be directly added in the form of their powder, which can prevent sedimentation during slurry mixing, and the particle size is relatively small.
- the small fourth LMFP material and the fifth LMFP material can be added either in the form of powder or in the form of slurries, wherein, in addition to organic solvents, the respective slurries can also contain dispersants, such as PVP etc.
- an embodiment of the present application further provides a positive electrode sheet, the positive electrode sheet includes a current collector and a positive electrode material layer disposed on the current collector, and the positive electrode material layer includes the above-mentioned positive electrode material Or coated with the above-mentioned positive electrode slurry.
- the positive electrode sheet containing the above positive electrode material has a high compaction density.
- the positive electrode material layer also includes a conductive agent and a binder.
- the positive electrode material layer can be formed by coating the above-mentioned positive electrode slurry on the current collector.
- an embodiment of the present application further provides a battery including the above positive electrode sheet.
- the battery also has excellent electrical properties such as higher capacity, lower probability of dissolving manganese, and higher cycle stability.
- the above-mentioned first to fifth LMFP materials are respectively denoted as particle 1, particle 2, particle 3, particle 4, particle 5, and 5 kinds of particles are selected according to the particle size and particle number ratio in Table 1, for subsequent mixing to obtain Positive electrode materials corresponding to different embodiments.
- the chemical formula of LMFP in particle 1 to particle 5 is LiMn 0.65 Fe 0.35 PO 4 .
- the test method for the particle size of each LMFP material is: the test equipment is a laser particle size analyzer, and the reference model is Malvern 2000/3000.
- the test method is as follows: each LMFP material is dispersed in deionized water, ultrasonicated for 10 min, and the particle refractive index is 1.74; the particle size D 50 of each LMFP material is obtained by testing.
- the method for measuring the number of particles of LMFP materials with different particle sizes is as follows: LMFP materials with different particle sizes are approximately spherical, and the mass of a single sphere is calculated according to the particle size D 50 and bulk density (about 3.6 g/cm 3 ) of each particle. By controlling the feeding quality of LMFP materials with different particle sizes, the number of particles of LMFP materials with different particle sizes is controlled.
- the test method for the median particle size of primary particles of each LMFP material is as follows: take a scanning electron microscope (SEM) photo of each LMFP material at a magnification of 10,000 times, measure the size of about 300 primary particles artificially, and make a number distribution. , to obtain the median diameter of the primary particles.
- SEM scanning electron microscope
- Preparation of positive electrode slurry add a certain proportion of organic solvent NMP and binder PVDF into the mixer, and after stirring for 1 hour, add conductive agent (specifically, carbon tubes with a mass ratio of 0.6:0.5:0.3, conductive carbon Mixing of black and graphene), stir for 30min, then add particle 1, particle 2 and particle 3 in the form of their respective powders, after stirring for 1.5h, add the PVP-containing NMP slurry of particle 4 and particle 5, and stir 1.5h, after sieving, the positive electrode slurry was obtained.
- the mass ratio of the positive electrode material composed of particles 1-particles 5 to the conductive agent, the binder PVDF, and the organic solvent NMP is 100:2:2:30.
- Preparation of positive electrode sheet The positive electrode slurry corresponding to each example was coated on both sides of the aluminum foil respectively, and after drying, a positive electrode material layer was formed on the aluminum foil to obtain an unpressed positive electrode sheet. into a size of 40*100mm, and then use a large hydraulic tablet machine to perform tablet compression to obtain a positive electrode tablet after tableting.
- the compaction density of the positive electrode sheet can be calculated according to the areal density of the positive electrode sheet and the thickness after pressing, and the results are summarized in Table 2.
- Preparation of the battery First, prepare the positive electrode slurry corresponding to each example into a single-sided positive electrode sheet with an areal density of 2.0 g/dm 2 and a compacted density of 2.65 g/cm 3 , and each single-sided positive electrode sheet was fabricated. 2025 coin cell battery.
- the positive electrode slurry corresponding to each embodiment was first prepared into a double-sided positive electrode sheet with an areal density of 4.0 g/dm 2 and a compacted density of 2.65 g/cm 3 ; and then provided with an areal density of 2.1 g/dm 2 and a compacted density It is a double-sided negative electrode sheet of 1.60 g/cm 3 ; the diaphragm is made of PP film, and the 053450 full battery is assembled.
- the test method of specific capacity is: charge the button battery corresponding to each embodiment at 0.1C under constant current and constant voltage until the voltage is 4.3V, and the cut-off current is 0.05C; then discharge under constant current and constant voltage to 0.1C The voltage was 2.5V, and the charge-discharge cycle was carried out 3 times. The discharge capacity after the third cycle was taken and divided by the amount of dressing of the positive electrode material layer on the positive electrode sheet to calculate the specific capacity of the battery.
- the test method of the rate performance is: at 25°C, the full battery corresponding to each example is first charged to 4.2V with a constant current of 0.2C, and then discharged to 2.5V with a constant current at different rates of 0.2C and 5C respectively, and the 5C is calculated.
- the ratio of the discharge capacity at 0.2C to the discharge capacity at 0.2C, and this ratio is used to measure the rate performance of the battery.
- the test method for the amount of dissolved Mn in the negative electrode is as follows: at 45°C, the full battery corresponding to each example is charged to 4.3V with a constant current of 1C, and then discharged to 2.5V with a constant current of 1C, after 500 charge-discharge cycles. , disassemble the battery, and test the Mn content in the negative electrode material of the negative pole piece; wherein the Mn content is measured by inductively coupled plasma-emission spectrometer (ICP).
- ICP inductively coupled plasma-emission spectrometer
- the compaction density of the positive electrode sheet can be reduced to 2.65 g. /cm 3 or more, the highest can reach 2.9g/cm 3 , the specific capacity of the battery is basically not significantly reduced, so that the battery can have a higher energy density.
- the positive electrode materials of the above embodiments can also make the battery have excellent rate performance, for example, the ratio of the discharge capacity at 5C to 0.2C is 84%-92%, and the battery can be cycled 500 times at 45°C The amount of dissolved Mn in the negative electrode was low, not exceeding 420 ppm.
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Abstract
Description
Claims (8)
- 一种正极材料,其中,所述正极材料包括第一磷酸锰铁锂材料、第二磷酸锰铁锂材料、第三磷酸锰铁锂材料、第四磷酸锰铁锂材料和第五磷酸锰铁锂材料,所述第一磷酸锰铁锂材料、所述第二磷酸锰铁锂材料、所述第三磷酸锰铁锂材料、所述第四磷酸锰铁锂材料和所述第五磷酸锰铁锂材料的颗粒数量比为(0.8-1.2):(0.8-1.2):(1.6-2.4):(6.4-9.6):(6.4-9.6);其中,所述第一磷酸锰铁锂材料为团聚体,所述第四磷酸锰铁锂材料和第五磷酸锰铁锂材料均为类单晶,所述第二磷酸锰铁锂材料和第三磷酸锰铁锂材料分别为团聚体和/或类单晶,且满足以下粒径关系:D 50 5<D 50 4<D 50 3<D 50 2<D 50 1,且D 50 2=aD 50 1,D 50 3=bD 50 1,D 50 4=cD 50 1,D 50 5=dD 50 1,5μm≤D 50 1≤15μm;其中,所述D 50 1至D 50 5依次表示所述第一磷酸锰铁锂材料至所述第五磷酸锰铁锂材料的粒径D 50的值,单位均为μm;所述a的取值范围为0.35-0.5,所述b的取值范围为0.2-0.27,所述c的取值范围为0.17-0.18,所述d的取值范围为0.15-0.16。
- 如权利要求1所述的正极材料,其中,所述a的取值范围为0.41-0.45;所述b的取值范围为0.21-0.23。
- 如权利要求1或2所述的正极材料,其中,所述a为0.41,所述b为0.23,所述c为0.18,所述d为0.16。
- 如权利要求1-3中任一项所述的正极材料,其中,所述第一磷酸锰铁锂材料、第二磷酸锰铁锂材料、第三磷酸锰铁锂材料、第四磷酸锰铁锂材料和第五磷酸锰铁锂材料的颗粒数量比为1:1:2:8:8。
- 如权利要求1-4中任一项所述的正极材料,其中,所述正极材料中,所述团聚体的一次颗粒的中值粒径在100nm-500nm的范围。
- 如权利要求1-5中任一项所述的正极材料,其中,所述正极材料中,所述类单晶的一次颗粒粒径在0.5μm-2.5μm的范围。
- 一种正极片,其中,所述正极片包括集流体和设置在所述集流体上的正极材料层,所述正极材料层包括如权利要求1-6中任一项所述的正极材料。
- 一种电池,其中,所述电池包括如权利要求7所述的正极片。
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